US6028035A - Substituted 4-benzoylpyrazoles - Google Patents

Substituted 4-benzoylpyrazoles Download PDF

Info

Publication number
US6028035A
US6028035A US09/331,671 US33167199A US6028035A US 6028035 A US6028035 A US 6028035A US 33167199 A US33167199 A US 33167199A US 6028035 A US6028035 A US 6028035A
Authority
US
United States
Prior art keywords
compounds
sub
differ
fact
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09/331,671
Other languages
English (en)
Inventor
Regina Luise Hill
Uwe Kardorff
Michael Rack
Norbert Gotz
Ernst Baumann
Wolfgang Von Deyn
Stefan Engel
Guido Mayer
Martina Otten
Joachim Rheinheimer
Matthias Witschel
Ulf Misslitz
Helmut Walter
Karl-Otto Westphalen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Assigned to BASF AKTIENGESELLSCHAFT reassignment BASF AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAUMANN, ERNST, ENGEL, STEFAN, GOETZ, NORBERT, HILL, REGINA LUISE, KARDORFF, UWE, MAYER, GUIDO, MISSLITZ, ULF, OTTEN, MARTINA, RACK, MICHAEL, RHEINHEIMER, JOACHIM, VON DEYN, WOLFGANG, WALTER, HELMUT, WESTPHALEN, KARL-OTTO, WITSCHEL, MATTHIAS
Application granted granted Critical
Publication of US6028035A publication Critical patent/US6028035A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C07D231/24—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms having sulfone or sulfonic acid radicals in the molecule

Definitions

  • R 1 , R 2 are hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, --OR 5 , --OCOR 6 , --OSO 2 R 6 , --SH, --S(O) n R 7 , --SO 2 OR 5 , --SO 2 NR 5 R 8 , --NR 8 SO 2 R 6 or --NR 8 COR 6 ;
  • R 3 is hydrogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, --OR 7 , --SR 7 or --NR 7 R 10 ;
  • R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 4 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, --COR 9 , --CO 2 R 9 , --COSR 9 or --CONR 8 R 9 , it being possible for the abovementioned alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals and R 9 of the radicals --COR 9 , --CO 2 R 9 , --COSR 9 and --CONR 8 R 9 to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
  • X is oxygen or NR 8 ;
  • n 0, 1 or 2;
  • R 5 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 6 is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl
  • R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 8 is hydrogen or C 1 -C 6 -alkyl
  • R 9 is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, phenyl or benzyl;
  • R 10 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • Q is a pyrazole of the formula II ##STR2## which is linked in the 4-position and where R 11 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following radicals:
  • R 12 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -haloalkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, phenylcarbonyl, phenylcarbonylmethyl, phenoxycarbonyl or phenylsulfonyl, the four last-mentioned substituents being unsubstituted or the phenyl ring being in each case partially or fully halogenated and/or having attached to it one to three of the following radicals:
  • R 13 is hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl
  • the invention relates to processes and intermediates for the preparation of compounds of the formula I, to compositions which comprise the latter, and to the use of the compounds of the formula I and of the compositions comprising them for controlling weeds.
  • herbicidal compositions which comprise the compounds I and which have a very good herbicidal activity.
  • processes for the preparation of these compositions and methods of controlling undesirable vegetation using the compounds I are also known.
  • the present invention also relates to stereoisomers of the compounds of the formula I. These include pure stereoisomers and mixtures of these.
  • the compounds of the formula I contain a carbon-nitrogen double bond and therefore exist in the form of E isomers or Z isomers or E/Z isomer mixtures. Furthermore, the compounds of the formula I may contain further carbon or carbon-nitrogen double bonds.
  • the invention relates both to the pure geometric isomers and to mixtures of these.
  • the compounds of the formula I may contain one or more chiral centers, in which case they exist in the form of enantiomers or diastereomer mixtures.
  • the invention relates both to the pure enantiomers or diastereomers and to the mixtures of these.
  • the compounds of the formula I may also be present in the form of their agriculturally useful salts, the type of salt generally being of no importance.
  • suitable salts are salts of those cations, or the acid addition salts of those acids, whose cations, or anions, respectively, do not adversely affect the herbicidal activity of the compounds I.
  • Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium where, if desired, one to four hydrogen atoms may be replaced by C 1 -C 4 -alkyl or hydroxy-C 1 -C 4 -alkyl and/or a phenyl or benzyl, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, moreover phosphonium ions, sulfonium ions, preferably tri(C 1 -C 4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri(C 1 -C 4 -alkyl)sulfoxonium.
  • Anions of useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 4 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, --COR 9 , --CO 2 R 9 , --COSR 9 or --CONR 8 R 9 , it being possible for the abovementioned alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals and R 9 of the radicals --COR 9 , --CO 2 R 9 , --COSR 9 and --CONR 8 R 9 to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
  • organic moieties mentioned for the substituents R 1 -R 13 or as radicals on phenyl, hetaryl and heterocyclyl rings are collective terms for individual enumerations of the individual group members.
  • All hydrocarbon chains ie. all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, alkyliminooxy, alkoxyamino, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, alkenyl, cycloalkenyl, alkynyl moieties can be straight-chain or branched.
  • halogenated substituents preferably have attached to them one to five identical or different halogen atoms, the meaning halogen being in each case fluorine, chlorine, bromine or iod
  • C 2 -C 4 -alkyl ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
  • C 1 -C 4 -haloalkyl a C 1 alkyl C 4 -alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropy
  • C 1 -C 4 -haloalkoxy a C 1 -C 4 -alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-
  • C 1 -C 4 -alkylsulfonyl (C 1 -C 4 -alkyl-S( ⁇ O) 2 --): methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;
  • C 1 -C 6 -alkylsulfonyl C 1 -C 4 -alkylsulfonyl as mentioned above, and also pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsul
  • C 1 -C 6 -haloalkylsulfonyl a C 1 -C 6 -alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie.
  • fluoromethylsulfonyl difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, pentafluoroethyls
  • C 1 -C 4 -alkyliminooxy methyliminooxy, ethyliminooxy, 1-propyliminooxy, 2-propyliminooxy, 1-butyliminooxy and 2-butyliminooxy;
  • C 3 -C 6 -alkenyl prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-mnethylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1yl, 3-en-1-yl, 3-en-1-yl, 1,1-dimethylprop
  • C 2 -C 6 -alkenyl C 3 -C 6 -alkenyl as mentioned above, and also ethenyl;
  • C 3 -C 6 -alkynyl prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl, pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4
  • C 2 -C 6 -alkynyl C 3 -C 6 -alkynyl as mentioned above, and also ethynyl:
  • C 3 -C 6 -cycloalkyl cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
  • C 4 -C 6 -cycloalkenyl cyclobuten-1-yl, cyclobuten-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclopenten-4-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;
  • heterocyclyl and also the heterocyclyl radicals in heterocyclyloxy: three- to seven-membered saturated or partially unsaturated mono- or polycyclic heterocycles which contain one to three hetero atoms selected from a group consisting of oxygen, nitrogen and sulfur, such as oxiranyl, oxetan-3-yl, thietan-3-yl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl
  • hetaryl and also the hetaryl radicals in hetaryloxy: aromatic mono- or polycyclic radicals which, besides carbon ring members, may additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, eg.
  • All phenyl, hetaryl and heterocyclyl rings are preferably unsubstituted or have attached to them one to three halogen atoms and/or one or two radicals selected from the following group: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl.
  • the variables preferably have the following meanings, viz. in each case alone or in combination:
  • R 1 is nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, --OR 5 or --S(O) n R 7 ;
  • nitro, halogen eg. fluorine, chlorine or bromine, C 1 -C 6 -haloalkyl, --OR 5 or --SO 2 R 7 , eg. methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl; particularly preferably nitro, fluorine, chlorine, bromine, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl;
  • R 2 is hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, --OR 5 or --S(O) n R 7 ;
  • R 3 is hydrogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or --OR 7 ;
  • R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl, it being possible for the 4 last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups: hydroxyl, mercapto, amino, cyano, --OR 10 , ⁇ NOR 10 , --OCOR 10 , --CO 2 R 10 , --COSR 10 , --CONR 8 R 10 , C 1 -C 4 -alkyliminooxy, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-C 2 -C 6 -alkoxycarbonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, it being
  • X is oxygen or NH
  • n 0 or 2;
  • R 5 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 8 is hydrogen or C 1 -C 6 -alkyl
  • R 10 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 11 is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl; especially preferably methyl, ethyl, propyl, isopropyl, butyl or isobutyl;
  • R 12 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -haloalkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, phenylcarbonylmethyl, or phenylsulfonyl, it being possible for the phenyl ring of the two last-mentioned substituents to be partially or fully halogenated and/or to have attached to it one to three of the following radicals: nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy;
  • R 13 is hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl; especially preferably hydrogen, methyl, ethyl or trifluoromethyl.
  • R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl, it being possible for the 4 last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups: hydroxyl, mercapto, amino, cyano, --OR 10 , ⁇ NOR 10 , --OCOR 10 , --CO 2 R 10 , --COSR 10 , --CONR 8 R 10 , C 1 -C 4 -alkyliminooxy, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-C 2 -C 6 -alkoxycarbonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, it being
  • R 2 is halogen or C 1 -C 4 -alkyl, in particular halogen
  • R 3 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen
  • R 4 is C 1 -C 6 -alkyl, C 3 -C 6 -alkynyl, it being possible for these two substituents to be partially or fully halogenated and/or to contain one to three of the following groups: phenyl or hetaryl, it being possible for these, in turn, to be partially or fully halogenated;
  • X is oxygen
  • R 11 is C 1 -C 6 -alkyl
  • R 12 is hydrogen
  • R 13 is hydrogen
  • the 4-benzoylpyrazoles of the formula I can be obtained by various routes, for example by the following processes:
  • L 1 is a nucleophilically displaceable leaving group, such as halogen, eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate and the like.
  • halogen eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate and the like.
  • the activated carboxylic acid can be employed directly, as in the case of the carboxylic acid halides, or prepared in situ, eg. with dicyclocarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfite/triphenylphosphine, carbonyldiimidazole and the like.
  • auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently employed in equimolar amounts. Under certain circumstances, a slight excess of the auxiliary base, for example 1.2 to 1.5 mol equivalents, based on II, may be advantageous.
  • Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates.
  • solvents which can be used are chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters such as ethyl acetate or mixtures of these.
  • carboxylic acid halides are employed as activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10° C. when adding this reactant. The mixture is subsequently stirred at 20-100° C., preferably at 25-50° C., until the reaction is complete. Work-up is carried out in the customary manner, for example the reaction mixture is poured into water and the product of value is extracted. Solvents which are especially suitable for this purpose are methylene chloride, diethyl ether and ethyl acetate. After the organic phase has been dried and the solvent has been numbered, the ester of the formula IV is purified, preferably by chromatography. Alternatively, it is possible to employ the crude enol ester of the formula IV for the rearrangement reaction without further purification.
  • solvents which can be used are acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures of these.
  • Preferred solvents are acetonitrile and dioxane.
  • Suitable bases are tertiary amines such as triethylamine, pyridine or alkali metal carbonates such as sodium carbonate, potassium carbonate, which are preferably employed in equimolar amounts or up to a four-fold excess, based on the ester. Triethylamine or alkali metal carbonates are preferably used.
  • Suitable cyano compounds are inorganic cyanides such as sodium cyanide, potassium cyanide and organic cyano compounds such as acetone cyanohydrin, trimethylsily [sic] cyanide. They are employed in an amount of 1 to 50 mol percent, based on the ester. Acetone cyanohydrin or trimethylsilyl cyanide are preferably employed, for example in an amount of 5 to 15, preferably 10, mol percent based on the ester.
  • Substances which are especially preferably employed are alkali metal carbonates such as potassium carbonate in acetonitrile or dioxane.
  • the reaction mixture is acidified with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, [lacuna] extracted with an organic solvent, eg. methylene chloride, ethyl acetate.
  • the organic extract [sic] can be extracted with 5-10% strength alkali metal carbonate solution, eg. sodium carbonate or potassium carbonate solution.
  • the aqueous phase is acidified, and the precipitate which forms is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated.
  • L 2 is a nucleophilically displaceable leaving group such as halogen, eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate, sulfonate, eg. mesylate, triflate and the like.
  • halogen eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate, sulfonate, eg. mesylate, triflate and the like.
  • the compounds of the formula V can be employed directly, for example in the case of the alkyl halides, carboxylic acid halides, sulfonyl halides, carboxylic anhydrides and sulfonic anhydrides, or prepared in situ, for example activiated carboxylic acids (by means of carboxylic acid and dicyclohexylcarbodiimide, carbonyldiimidazole and the like).
  • the starting compounds are employed in an equimolar ratio. However, it may also be advantageous to employ one or the other component in an excess.
  • auxiliary base it may be advantageous to carry out the reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently employed in equimolar amounts in this case.
  • an excess of the auxiliary base for example 1.5 to 3 mol equivalents, based on II, may be advantageous.
  • Suitable auxiliary bases are tertiary alkylamines such as triethylamine, pyridine, alkali metal carbonates, eg. sodium carbonate, potassium carbonate and alkali metal hydrides, eg. sodium hydride. Substances which are preferably used are triethylamine, pyridine and potassium carbonate.
  • suitable solvents are chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons, eg. toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide or esters such as ethyl acetate, or mixtures of these.
  • chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons, eg. toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide
  • reaction temperature is in the range of from 0° C. to the boiling point of the reaction mixture.
  • Work-up can be effected in a manner known per se to give the product.
  • R 1 , R 2 are hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, --OR 5 , --OCOR 6 , --OSO 2 R 6 , --SH, --S(O) n R 7 , --SO 2 OR 5 , --SO 2 NR 5 R 8 , --NR 8 SO 2 R 6 or --NR 8 COR 6 ;
  • R 3 is hydrogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, --OR 7 , --SR 7 or --NR 7 R 10 ;
  • R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 4 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, --COR 9 , --CO 2 R 9 , --COSR 9 or --CONR 8 R 9 , it being possible for the abovementioned alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals and R 9 of the radicals --COR 9 , --CO 2 R 9 , --COSR 9 and --CONR 8 R 9 to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
  • X is oxygen or NR 8 ;
  • n 0, 1 or 2;
  • R 5 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 6 is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl
  • R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 8 is hydrogen or C 1 -C 6 -alkyl
  • R 9 is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, phenyl or benzyl;
  • R 10 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
  • R 14 is hydroxyl or a radical which can be removed by hydrolysis.
  • radicals which can be removed by hydrolysis are alkoxy, phenoxy, alkylthio and phenylthio radicals which can be substituted, halides, hetaryl radicals which are bonded via nitrogen, amino and imino radicals which can be substituted, and the like.
  • L is halogen, in particular chlorine or bromine.
  • M is C 1 -C 6 -alkoxy.
  • halogenating agents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.
  • the benzoic esters of the formula III ⁇ can be obtained by various routes, for example by one of the following processes: ##STR701##
  • Isophthalic acid derivatives of the formula VII can be obtained by oxidizing aldehydes of the formula VI in a manner known per se (J. March, "Advanced Organic Chemistry", 1985, 3rd Edition, p. 629 et seq., Wiley-Interscience Publication).
  • the compounds of the formula VII can first be converted into the corresponding activated carboxylic acids VIII in which L 3 is a nucleophilically displaceable leaving group such as halogen, eg. bromine, chlorine, hetaroyl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate and the like, by methods similar to those known from the literature, and the products can subsequently be converted into the corresponding hydroxamic acid or carbohydrazide derivatives of the formula IX (Australian J. Chem. (1969), 22, 1731-1735; ibid (1969), 22, 161-173; J. Org. Chem. (1974), 27, 1341-1349).
  • L 3 is a nucleophilically displaceable leaving group such as halogen, eg. bromine, chlorine, hetaroyl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, triflu
  • Nitriles of the formula XI can be converted into imino esters by alcoholysis (R 7 OH) in a manner known per se, and these imino esters can be converted in a further step with hydroxylamines or hydrazines to give compounds of the formula III ⁇ (J. March, "Advanced Organic Chemistry", 1985, 3rd Edition, pp. 792-793, Wiley-Interscience Publication; U.S. Pat. No. 4,965,390).
  • nitriles of the formula XI can be synthesized by methods similar to those known from the literature starting from the corresponding aldehydes VI (J. March, "Advanced Organic Chemistry", 1985, 3rd Edition, pp. 806-807, Wiley-Interscience Publication). Equally, it is possible to obtain nitriles of the formula XI from anilines of the formula XII by means of Sandmeyer reaction or from aryl halides of the formula XIII by Rosemund/von Braun reaction with metal cyanides, in particular CuCN (J. March, "Advanced Organic Chemistry", 1985, 3rd Edition, p. 594, p. 648, Wiley-Interscience Publication). ##STR704##
  • aldehydes of the formula VI can be synthesized from corresponding toluenes of the formula XIV by processes similar to those known from the literature, by converting them into the ⁇ -halotoluene XV and subsequently oxidizing the product (cf. Synth. Commun. 22 (1992), 1967-1971). ##STR705##
  • the residue was taken up in 50 ml of dry acetonitrile, treated with 1.20 g (0.0087 mol) of finely pulverulent calcium carbonate and refluxed for 3.5 hours. After cooling, the solvent was removed in vacuo and the residue was taken up in water. The aqueous phase was brought to pH 1-2 using 10% strength hydrochloric acid solution and extracted with ethyl acetate. The combined organic phases were subsequently washed to neutrality with water and dried, and the solvent was distilled off in vacuo.
  • Step c) 2-Chloro-3-methyl-4-methylsulfonylbenzoic acid 82 g (0.33 mol) of 2-chloro-3-methyl-4-methylsulfonylacetophenone were dissolved in 700 ml of dioxane, and 1 l of a 12.5% strength sodium hypochlorite solution was added at room temperature. Stirring was subsequently continued for 1 hour at 80° C. After cooling, two phases formed, of which the bottom phase was diluted with water and slightly acidified. The solid which had precipitated was washed with water and dried. This gave 60 g (73% of theory) of 2-chloro-3-methyl-4-methylsulfonylbenzoic acid.
  • the pH was then brought to 1 using 10% strength hydrochloric acid, and 1500 ml of aqueous 40% strength sodium hydrogen sulfite solution were added. After the mixture had been stirred for 1 hour at room temperature, the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with sodium hydrogen sulfite solution and dried. After the solvent had been distilled off, 102.0 g of methyl 2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate were obtained.
  • the 4-benzoylpyrazoles of the formula I and their agriculturally useful salts are suitable as herbicides, both in the form of stereoisomer mixtures and in the form of the pure stereoisomers.
  • the herbicidal compositions comprising compounds of the formula I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, soybeans and cotton they act against broad-leaved weeds and grass weeds without damaging the crop plants substantially. This effect is observed especially at low rates of application.
  • the 4-benzoylpyrazoles of the formula I, or compositions comprising them can additionally be employed in a further number of crop plants for eliminating undesirable plants.
  • suitable crops are the following: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var.
  • the compounds of the formula I can also be used in crops which tolerate the action of herbicides due to breeding including genetic engineering methods.
  • the compounds of the formula I, or the herbicidal compositions comprising them can be employed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • directly sprayable aqueous solutions, powders, suspensions also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
  • the herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or of an agriculturally useful salt of I and auxiliaries conventionally used for the formulation of crop protection products.
  • Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, eg. amines such as N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthal
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the subsrates [sic] as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier.
  • Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylaryl sulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxy
  • Powders, materials for spreading and dusts can be prepared by mixing or concommitantly grinding the active substances with a solid carrier.
  • Granules eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
  • the concentrations of the compounds of the formula I in the ready-to-use products can be varied within wide ranges.
  • the formulations comprise approximately from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • the compounds I according to the invention can be formulated for example as follows:
  • V. 3 parts by weight of the active ingredient No. 2.01 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active ingredient.
  • the active ingredients I can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spray apparatus, in such a way that they come into as little contact, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil (post-directed, lay-by).
  • the compounds of the formula I can be mixed and applied jointly with a large number of representatives of other groups of herbicidal or growth-regulatory active ingredients.
  • Suitable components in mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, hetaryloxyalkanoic acid [sic] and its derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF 3 -phenylderivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives
  • the compounds the formula I alone or in combination with other herbicides, in the form of a mixture with additional other crop protection agents, for example with agents for controlling pests, phytopathogenic fungi or bacteria.
  • additional other crop protection agents for example with agents for controlling pests, phytopathogenic fungi or bacteria.
  • miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies.
  • Non-phytotoxic oils and oil concentrates can also be added.
  • the rates of application of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha active substance (a.s.)
  • the culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as substrate.
  • the seeds of the test plants were sown separately for each species.
  • the active ingredients suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles.
  • the containers were irrigated gently to promote germination and growth and subsequently covered with translucent plastic hoods until the plants had rooted. This cover causes [sic] uniform germination of the test plants unless this was adversely affected by the active ingredients.
  • test plants were first grown to a plant height of from 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
  • the rate of application for the post-emergence treatment was 0.125 and 0.0625 kg/ha a.s. (active substance).
  • the plants were kept at from 10-25° C. and 20-35° C., respectively.
  • the test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
  • Evaluation was carried out using a scale of from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage or normal course of growth.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
US09/331,671 1997-01-03 1997-12-19 Substituted 4-benzoylpyrazoles Expired - Fee Related US6028035A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19700096A DE19700096A1 (de) 1997-01-03 1997-01-03 Substituierte 4-Benzoyl-pyrazole
DE19700096 1997-01-03
PCT/EP1997/007210 WO1998029392A1 (de) 1997-01-03 1997-12-19 Substituierte 4-benzoyl-pyrazole

Publications (1)

Publication Number Publication Date
US6028035A true US6028035A (en) 2000-02-22

Family

ID=7816804

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/331,671 Expired - Fee Related US6028035A (en) 1997-01-03 1997-12-19 Substituted 4-benzoylpyrazoles

Country Status (24)

Country Link
US (1) US6028035A (cs)
EP (1) EP0960100B1 (cs)
JP (1) JP4242454B2 (cs)
KR (1) KR100523311B1 (cs)
CN (1) CN1106385C (cs)
AR (1) AR011354A1 (cs)
AT (1) ATE244705T1 (cs)
AU (1) AU744201B2 (cs)
BR (1) BR9714257A (cs)
CA (1) CA2276463C (cs)
CZ (1) CZ297520B6 (cs)
DE (2) DE19700096A1 (cs)
DK (1) DK0960100T3 (cs)
EA (1) EA002421B1 (cs)
ES (1) ES2203832T3 (cs)
HU (1) HUP0000491A3 (cs)
IL (1) IL130600A (cs)
NZ (1) NZ336452A (cs)
PL (1) PL193702B1 (cs)
PT (1) PT960100E (cs)
SK (1) SK284921B6 (cs)
UA (1) UA56209C2 (cs)
WO (1) WO1998029392A1 (cs)
ZA (1) ZA987B (cs)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040236146A1 (en) * 2001-09-11 2004-11-25 Hansjorg Lehmann Method for producing 3-bromomethylbenzoic acids
US10785979B2 (en) 2015-08-25 2020-09-29 Bayer Cropscience Aktiengesellschaft Substituted ketoxime benzoylamides

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006076885A (ja) * 2002-09-13 2006-03-23 Nippon Soda Co Ltd イミノ基を有するベンゾイル化合物及び除草剤
AR056889A1 (es) 2005-12-15 2007-10-31 Ishihara Sangyo Kaisha Compuestos benzoilpirazol y herbicidas que los contienen
US8957096B2 (en) * 2011-11-03 2015-02-17 Bayer Intellectual Property Gmbh Herbicidally active oxime-ether-substituted benzoylamides
EP2907807A1 (en) 2014-02-18 2015-08-19 Basf Se Benzamide compounds and their use as herbicides

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063925A (en) * 1974-03-28 1977-12-20 Sankyo Company Limited Herbicidal compositions
US4146726A (en) * 1974-03-28 1979-03-27 Sankyo Company Limited Pyrazole sulfonates
GB2122188A (en) * 1982-04-24 1984-01-11 Nissan Chemical Ind Ltd Pyrazole derivative
EP0203428A1 (en) * 1985-05-11 1986-12-03 Nissan Chemical Industries Ltd. Herbicidal 4-benzoyl-1-alkyl(alkenyl)-pyrazoles
US4643757A (en) * 1985-05-20 1987-02-17 Nissan Chemical Industries, Ltd. Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles
EP0282944A2 (en) * 1987-03-17 1988-09-21 Nissan Chemical Industries Ltd. Pyrazole derivative and herbicide containing it
EP0344775A1 (en) * 1988-06-03 1989-12-06 Nissan Chemical Industries Ltd. Process for producing 4-benzoyl-5-hydroxypyrazoles

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56147772A (en) * 1980-04-18 1981-11-16 Ishihara Sangyo Kaisha Ltd Preparation of 4-benzoylpyrazole compound

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063925A (en) * 1974-03-28 1977-12-20 Sankyo Company Limited Herbicidal compositions
US4146726A (en) * 1974-03-28 1979-03-27 Sankyo Company Limited Pyrazole sulfonates
US4261729A (en) * 1974-03-28 1981-04-14 Sankyo Company Limited Herbicidal compositions and pyrazole derivatives
US4414392A (en) * 1974-03-28 1983-11-08 Sankyo Company, Ltd. Herbicidal compositions and pyrazole derivatives
US4508910A (en) * 1974-03-28 1985-04-02 Sankyo Company Ltd. Herbicidal 4-benzoyl-5-hydroxy-pyrazales
US4687858A (en) * 1974-03-28 1987-08-18 Sankyo Company Limited Organic acid esters of 4-benzoyl-5-hydroxy(mercapto)pyrazoles
GB2122188A (en) * 1982-04-24 1984-01-11 Nissan Chemical Ind Ltd Pyrazole derivative
EP0203428A1 (en) * 1985-05-11 1986-12-03 Nissan Chemical Industries Ltd. Herbicidal 4-benzoyl-1-alkyl(alkenyl)-pyrazoles
US4643757A (en) * 1985-05-20 1987-02-17 Nissan Chemical Industries, Ltd. Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles
EP0282944A2 (en) * 1987-03-17 1988-09-21 Nissan Chemical Industries Ltd. Pyrazole derivative and herbicide containing it
EP0344775A1 (en) * 1988-06-03 1989-12-06 Nissan Chemical Industries Ltd. Process for producing 4-benzoyl-5-hydroxypyrazoles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Tanaka er al, Chemical Abstracts , vol. 129:302,634, 1998. *
Tanaka er al, Chemical Abstracts, vol. 129:302,634, 1998.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040236146A1 (en) * 2001-09-11 2004-11-25 Hansjorg Lehmann Method for producing 3-bromomethylbenzoic acids
US10785979B2 (en) 2015-08-25 2020-09-29 Bayer Cropscience Aktiengesellschaft Substituted ketoxime benzoylamides

Also Published As

Publication number Publication date
JP4242454B2 (ja) 2009-03-25
CZ297520B6 (cs) 2007-01-03
HUP0000491A2 (hu) 2000-06-28
ES2203832T3 (es) 2004-04-16
EA199900612A1 (ru) 2000-02-28
KR20000062415A (ko) 2000-10-25
CN1106385C (zh) 2003-04-23
DK0960100T3 (da) 2003-11-03
EA002421B1 (ru) 2002-04-25
IL130600A (en) 2003-01-12
AR011354A1 (es) 2000-08-16
BR9714257A (pt) 2000-04-18
KR100523311B1 (ko) 2005-10-24
EP0960100B1 (de) 2003-07-09
DE59710430D1 (de) 2003-08-14
ZA987B (en) 1999-07-02
IL130600A0 (en) 2000-06-01
CZ239399A3 (cs) 2000-09-13
ATE244705T1 (de) 2003-07-15
CA2276463C (en) 2007-07-10
PT960100E (pt) 2003-11-28
DE19700096A1 (de) 1998-07-09
HUP0000491A3 (en) 2001-12-28
JP2001508421A (ja) 2001-06-26
NZ336452A (en) 2001-06-29
AU744201B2 (en) 2002-02-21
PL193702B1 (pl) 2007-03-30
WO1998029392A1 (de) 1998-07-09
EP0960100A1 (de) 1999-12-01
PL334546A1 (en) 2000-03-13
SK284921B6 (sk) 2006-02-02
SK86899A3 (en) 2000-01-18
AU6090898A (en) 1998-07-31
CN1247532A (zh) 2000-03-15
CA2276463A1 (en) 1998-07-09
UA56209C2 (uk) 2003-05-15

Similar Documents

Publication Publication Date Title
US5883250A (en) Substituted azadioxacycloalkenes, fungicidal composition containing them, process for preparing them, and method of using them to combat fungi
US4999045A (en) Heterocyclic sulfonamides
US6077814A (en) 1-Substituted 4-carbamoyl-1,2,4-triazol-5-one derivatives and herbicide
US5457134A (en) Fluoroalkenyl compounds and their use as pest repellents
US5574064A (en) Amino-acid amide derivatives, agricultural or horticultural fungicides, and method for producing the same
US6080775A (en) Sulphonyl-mercapto-triazolyl derivatives and their use as microbicides
US4837217A (en) Pyridazinone derivatives, preparation thereof, and insecticidal, acaricidal, nematicidal, fungicidal compositions
US4909827A (en) Herbicidal compositions based on substituted pyrazolin-5-one derivatives and use thereof
US4549900A (en) Combating fungi with substituted 1-azolyl-butan-2-ones and -2-ols
US5086183A (en) Substituted pyrazoline derivatives
US5021082A (en) Herbicidal substituted sulphonylaminoazoles
US4503059A (en) 1,3-Dioxacyclopentanes, their pesticidal use and compositions for pesticidal use
US4968687A (en) Pesticidal substituted 4-heterocyclyloximino-pyrazolin-5-ones, compositions and use
US5080710A (en) Novel n-aryltetrahydrophthalimide compounds
US6028035A (en) Substituted 4-benzoylpyrazoles
US4964895A (en) Substituted 4-(4-nitrophenoxy) pyrazoles and their use as herbicides
US5180418A (en) Herbicidally active thiadiazabicyclononanes and nonenes
US6143696A (en) Substituted 4-(3-alkenylbenzoyl)pyrazoles
US4039680A (en) Insecticidal substituted acetate compounds
US4966902A (en) Heterocyclic neophane analogs, processes for their preparation and their use as pest-combating agents
US5650374A (en) Herbicidal 1-cyclopropyl tetrazolinones
US5002957A (en) Azaneophyl sulfides, and their use as pesticides
US4980345A (en) Pyrazole compounds and use thereof
US5677465A (en) Benzaldehyde oxime derivatives, production and use thereof
US4725305A (en) N'-(substituted-1,3,5-triazin-2-yl)-N"-substituted-N",N"'-bis-(substituted-benzenesulphonyl)-guanidines as herbicides

Legal Events

Date Code Title Description
AS Assignment

Owner name: BASF AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HILL, REGINA LUISE;KARDORFF, UWE;RACK, MICHAEL;AND OTHERS;REEL/FRAME:010132/0581

Effective date: 19981201

CC Certificate of correction
FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20120222